Structures of the mono­fluoro- and mono­chloro­phenols at low temperature and high pressure

2-Fluorophenol, 3-fluorophenol and 3-chlorophenol were recrystallized from frozen solids at 260, 263 and 283 K. All compounds were also crystallized by the application of high pressure (0.36, 0.12 and 0.10 GPa). While 3-fluorophenol and 3-chlorophenol yielded the same phases under both conditions, different polymorphs were obtained for 2-fluorophenol. 4-Chlorophenol was crystallized both from the melt and from benzene to yield two different ambient-pressure polymorphs; crystallization from the melt at 0.02 GPa yielded the same phase as from benzene at ambient pressure. 3-Fluorophenol is unusual in forming a hydrogen-bonded chain along a 2₁ screw axis. Such behaviour is usually only observed for small alcohols, but here it appears to be stabilized by intermolecular C—H⋯F hydrogen-bond formation. 3-Chlorophenol is a more typical large alcohol and emulates a fourfold screw axis with two independent molecules positioned about a 2₁ axis, although there are significant distortions from this ideal geometry. The two phases of 4-chlorophenol consist of chains or rings connected by C—Cl⋯H interactions. The low-temperature and high-pressure polymorphs of 2-fluorophenol consist of chains of molecules connected through OH⋯OH hydrogen bonds; while inter-chain C—H⋯F interactions are significant at high pressure, there are none in the low-temperature form.

1. Introduction

Packing in alcohols has been studied by Brock & Duncan (1994) and subsequently by Taylor & Macrae (2001). Both studies showed that the size of the R-group attached to the alcohol functionality is a major factor in the packing behaviour of the molecules. We have recently investigated (Oswald et al., 2005) the effect of high pressure on the crystal structures of phenol (Allan et al., 2002), 2-chlorophenol and 4-fluoro­phenol, which all exhibit polymorphic behaviour on application of pressure. At ambient pressure 2-chlorophenol and 4-fluorophenol crystallize in high-symmetry space groups with the molecules disposed about 3₂ and symmetry operators; phenol packs via a pseudo-threefold axis in P2₁. All three systems crystallize under pressure in low-symmetry space groups with the molecules disposed about 2₁ screw axes. Fig. 1 illustrates the change in structure between ambient and high pressure for 2-chlorophenol. At ambient pressure the molecules adopt an arrangement in which the halophenyl group behaves as a bulky substituent. At high pressure, both compounds undergo a phase transition to a packing motif characteristic of a small alcohol. This paper describes the crystal structure determination of the remaining chloro- and fluorophenols at low temperature and high pressure to investigate whether the packing behaviour of these phenols can be altered with the application of pressures < 1 GPa.

Figure 1 (a) Crystal structures of 2-chlorophenol at ambient pressure and 100 K. Helices are formed about 32 axes by OH⋯OH hydrogen-bond formation. (b) The crystal structure of 2-chlorophenol at 0.12 GPa. The application of pressure changes the behaviour of the chlorophenyl substituent so that chains are formed where molecules are related by a 21 screw axis. Colour scheme: C black, Cl green, H light turquoise, O red.

2. Experimental

All samples were obtained from Sigma–Aldrich and used as received.

2.1. Low-temperature crystal growth

2-Fluorophenol (m.p. 289 K), 3-fluorophenol (m.p. 287 K) and 3-chlorophenol (m.p. 306 K) were each drawn into a capillary, and polycrystalline masses obtained by freezing at 260, 263 and 283 K, respectively. The samples were then recrystallized using the laser-assisted procedure of Boese & Nussbaumer (1994). All capillaries (o.d. 0.32–0.52 mm) were hand-drawn from 4 mm o.d. Pyrex^® glass tube. Phase I of 4-chlorophenol (m.p. 316 K) was obtained by melting a sample in a vial and leaving it to recrystallize at room temperature. Small, colourless crystals appeared on the side of the vial. Colourless crystals of phase II of 4-chlorophenol were obtained by holding a saturated benzene solution at 277 K.

2.2. Crystal structure determination at low temperature

X-ray diffraction intensities were collected with Mo Kα radiation on a Bruker Smart Apex CCD diffractometer equipped with an Oxford Cryosystems Cryostream-Plus variable-temperature device (Cosier & Glazer, 1986) and an OHCD laser-assisted crystallization device. Absorption corrections were carried out using the multiscan procedure SADABS (Sheldrick, 2004, based on the procedure described by Blessing, 1995). All the structures were solved by direct methods (SIR92; Altomare et al., 1993) and refined by full-matrix least-squares against F² using all data (CRYSTALS; Betteridge et al., 2003). H atoms were attached to C atoms in calculated positions and allowed to ride on their parent atoms. H atoms involved in hydrogen bonding were located in difference maps and refined with distance restraints. All non-H atoms were modelled with anisotropic displacement parameters.

2.3. High pressure: general procedures

Pressure was applied to the samples using a Merrill–Bassett diamond anvil cell (DAC; Merrill & Bassett, 1974) equipped with 600 µm culets, a tungsten gasket with a 300 µm hole, beryllium backing disks and a chip of ruby for pressure measurement. Pressures were measured by the ruby-fluorescence method by excitation with a 632.817 nm line from a He–Ne laser using a Jobin–Yvon LabRam 300 Raman spectrometer.

2.4. High-pressure crystal growth

The samples were loaded as liquids into the cell. In the case of 4-chloro- and 4-fluorophenol, both the sample and the cell were heated with a hot-air gun before loading to prevent crystallization at ambient temperature. In each case, pressure was applied until a polycrystalline mass was produced; the temperature of the cell was increased using a hot-air gun until a single crystallite remained. Slow cooling to ambient temperature yielded a single crystal that filled the entire gasket hole. Crystallization was monitored visually using a polarizing microscope. The crystallization pressures for each sample were as follows: 3-chlorophenol, 0.10 GPa; 3-fluorophenol, 0.12 GPa; 4-chlorophenol, 0.02 GPa; 2-fluorophenol, 0.36 GPa.

2.5. Crystal structure determinations at high pressure

Data were collected on a Bruker SMART APEX diffractometer with Mo Kα radiation. The collection and processing procedures followed were those described by Dawson et al. (2004).

Shading by the body of the DAC leads to low data completeness for crystals belonging to low-symmetry crystal systems. In all cases, except 2-fluorophenol, datasets were collected with the cell mounted in two different orientations in order to improve completeness. The diffraction patterns were indexed with the program GEMINI (Sparks, 2000). Data integration (to 2θ = 45°) was performed using SAINT (Bruker–Nonius, 2003) with dynamic masking to account for the shading from the DAC steel body (ECLIPSE; Parsons, 2004a). The program SHADE (Parsons, 2004b) was also used to take account of absorption effects of the diamonds and beryllium; further systematic errors were treated using SADABS before merging in SORTAV (Blessing, 1997).

The phases obtained for 3-fluorophenol, 3-chlorophenol and 4-chlorophenol corresponded to compressed forms of known ambient-pressure phases. Refinement against the high-pressure data therefore used the ambient-pressure coordinates as a starting model.

The structures were refined by full-matrix least-squares against F² (CRYSTALS) using all data. Free refinement of the positional parameters of the non-H atoms yielded carbon–carbon bond lengths varying from 1.34 to 1.40 Å. The phenyl rings were therefore constrained to be rigid hexagons. H atoms were attached to C atoms in calculated positions. The hydroxyl H atom, which is involved in hydrogen bonding, was geometrically placed except for 4-chlorophenol where the hydroxyl hydrogen was identified from the difference map and refined with distance and angular restraints. All oxygen and halogen atoms were modelled with anisotropic displacement parameters. The refinement of the crystal structure of 3-fluorophenol was subject to distance and angle restraints. 2-Fluorophenol, 3-chlorophenol and 4-chlorophenol were refined so that chemically similar bond distances and angles were subject to similarity restraints.

2.6. 2-Fluorophenol

Several attempts to grow a single crystal of 2-fluorophenol at high pressure resulted in the crystal fracturing after cooling to ambient temperature. Although the diffraction patterns obtained from these samples were characterized by broad, split reflections, they could, nevertheless, be indexed on an orthorhombic unit cell with the dimensions: a = 5.8952 (17), b = 10.9466 (19), c = 16.459 (4) Å. This is different to the cell obtained at 150 K (see Table 1). A solution was obtained using DASH (David et al., 2001; see below), but after refinement the residual remained in the region of R₁ = 0.17. The refined structure, which contains two molecules in the asymmetric unit in the space group P2₁2₁2₁, was characterized by high displacement parameters (0.2–0.3 Ų) on the F atoms, while the data, although strong at low angle, had no significant intensity above about 2θ = 35°. These observations imply that at 0.36 GPa and room temperature 2-fluorophenol forms a disordered phase. Difference maps failed to provide any clue as to how the structure might be better modelled, probably because of the relatively low completeness or poor reflection peak shapes. Since we are unable to improve modelling of the data, no further details on this phase are reported here.

Table 1
Experimental table

Weighting scheme: p = P(6)*max(F_o²,0) + (1 − P(6))F_c². Method = SHELXL97 (Sheldrick, 1997).

	3-Fluorophenol at 150 K (3F)	3-Fluorophenol at 0.12 GPa (3FP)	3-Chlorophenol at 150 K (3CL)	3-Chlorophenol at 0.1 GPa (3CLP)	4-Chlorphenol phase I at 150 K (4CL1)
Crystal data
Chemical formula	C6H5FO	C6H5FO	C6H5ClO	C6H5ClO	C6H5ClO
Mr	112.10	112.10	128.56	128.56	128.56
Cell setting, space group	Monoclinic, P21	Monoclinic, P21	Orthorhombic, P212121	Orthorhombic, P212121	Monoclinic, P21/c
a, b, c (Å)	5.6510 (12), 5.0642 (10), 9.3185 (19)	5.6747 (9), 5.0760 (4), 9.4753 (13)	3.9846 (5), 13.9272 (19), 20.699 (3)	4.0949 (4), 13.875 (3), 20.716 (3)	8.7086 (11), 15.4523 (19), 8.7414 (11)
β (°)	107.518 (4)	107.832 (11)	90	90	93.954 (2)
V (Å^3)	254.31 (9)	259.82 (6)	1148.7 (3)	1177.0 (3)	1173.5 (3)
Z	2	2	8	8	8
Dx (Mg m^−3)	1.464	1.433	1.487	1.451	1.455
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα	Mo Kα
No. of reflections for cell parameters	711	398	1504	983	3307
θ range (°)	2–28	5–23	5–25	3–23	2–29
μ (mm^−1)	0.12	0.12	0.55	0.53	0.53
Temperature (K)	150	293	150	293	150
Crystal form, colour	Cylinder, colourless	Blocks, colourless	Rod, colourless	Colourless, block	Block, colourless
Crystal size (mm)	1.00 × 0.32 × 0.32	0.30 × 0.30 × 0.18	0.90 × 0.10 × 0.10	0.30 × 0.30 × 0.18	0.44 × 0.38 × 0.25
Data collection
Diffractometer	Bruker SMART	Bruker SMART	Bruker SMART	Bruker SMART	Bruker SMART
Data collection method	ω scans	ω scans	ω scans	ω scans	ω scans
Absorption correction	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)
Tmin	0.67	0.67	0.22	0.85	0.69
Tmax	0.96	0.98	0.95	0.91	0.88
No. of measured, independent and observed reflections	1603, 672, 608	1310, 159, 146	4548, 1987, 1376	6533, 780, 476	7471, 2839, 2442
Criterion for observed reflections	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)
Rint	0.014	0.041	0.052	0.147	0.024
θmax (°)	28.6	23.2	25.0	23.3	28.8
Range of h, k, l	−6 → h → 7	−1 → h → 2	−4 → h → 4	0 → h → 4	−9 → h → 11
	−6 → k → 6	−5 → k → 0	−16 → k → 15	0 → k → 13	−20 → k → 19
	−12 → l → 9	−10 → l → 0	−24 → l → 22	0 → l → 21	−11 → l → 10
Refinement
Refinement on	F^2	F^2	F^2	F^2	F^2
R[F^2 > 2σ(F^2)], wR(F^2), S	0.037, 0.092, 1.05	0.064, 0.160, 1.15	0.069, 0.143, 0.94	0.098, 0.244, 0.99	0.039, 0.101, 0.74
No. of reflections	672	159	1977	780	2839
No. of parameters	77	32	152	62	152
H-atom treatment	Mixture of independent and constrained refinement	Not refined	Mixture of independent and constrained refinement	Not refined	Mixture of independent and constrained refinement
Weighting scheme	w = 1/[σ^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)sin θ]; P(i) are: 0.553E ^−1; 0.625E^−3, 0.00, 0.00, 0.00, 0.333	w = 1/[σ^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)sin θ]; P(i) are: 0.694E^−1, 0.349, 0.00, 0.00, 0.00, 0.333	w = 1/[σ^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)sin θ]; P(i) are: 0.00, 0.00, 0.00, 0.00, 0.00, 0.333	w = 1/[σ^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)sin θ]; P(i) are: 0.106, 5.04, 0.00, 0.00, 0.00, 0.333	w = 1/[σ^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)sin θ]; P(i) are: 0.684E^−1, 0.725, 0.00, 0.00, 0.00, 0.333
(Δ/σ)max	< 0.0001	< 0.0001	< 0.0001	0.004	0.001
Δρmax, Δρmin (e Å^−3)	0.22, −0.22	0.17, −0.16	0.56, −0.58	0.59, −0.56	0.33, −0.31
Extinction method	None	None	None	None	Larson (1970)
Extinction coefficient	–	–	–	–	45 (11)

	4-Chlorophenol phase II at 150 K (4CL2)	4-Chlorophenol phase II at 0.02 GPa (4CL2P)	2-Fluorophenol phase I at 150 K (2F1)	2-Fluorophenol phase II at 0.36 GPa and 403 K (2F2P)
Crystal data
Chemical formula	C6H5ClO	C6H5ClO	C6H5FO	C6H5FO
Mr	128.56	128.56	112.10	112.10
Cell setting, space group	Monoclinic, P21/c	Monoclinic, P21/c	Monoclinic, C2/c	Orthorhombic, P212121
a, b, c (Å)	3.9724 (5), 12.7328 (17), 23.155 (3)	4.1096 (4), 12.7665 (10), 23.181 (3)	17.1336 (10), 8.2766 (5), 11.4975 (7)	5.7168 (7), 9.9997 (19), 17.868 (2)
β (°)	94.126 (2)	94.201 (14)	100.234 (2)	90
V (Å^3)	1168.2 (3)	1212.9 (2)	1604.50 (17)	1021.4 (3)
Z	8	8	12	8
Dx (Mg m^−3)	1.462	1.408	1.392	1.458
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
No. of reflections for cell parameters	2464	1170	2044	397
θ range (°)	3–28	3–19	2–26	3–20
μ (mm^−1)	0.54	0.52	0.12	0.12
Temperature (K)	150	293	150	403
Crystal form, colour	Plate, colourless	Block, colourless	Cylinder, colourless	Plate, colourless
Crystal size (mm)	0.70 × 0.50 × 0.36	0.30 × 0.30 × 0.18	1.00 × 0.38 × 0.38	0.30 × 0.30 × 0.18
Data collection
Diffractometer	Bruker SMART	Bruker SMART	Bruker SMART	Bruker SMART
Data collection method	ω scans	ω scans	ω scans	ω scans
Absorption correction	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)
Tmin	0.49	0.68	0.575	0.96
Tmax	0.82	0.91	1.000	0.98
No. of measured, independent and observed reflections	7449, 2843, 2219	7359, 711, 397	7505, 1957, 1302	3070, 469, 261
Criterion for observed reflections	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)
Rint	0.016	0.063	0.021	0.099
θmax (°)	28.9	23.2	28.7	23.3
Range of h, k, l	−4 → h → 5	−4 → h → 4	−22 → h → 22	0 → h → 6
	−14 → k → 17	0 → k → 14	−10 → k → 11	0 → k → 5
	−31 → l → 29	0 → l → 10	−15 → l → 15	0 → l → 19
Refinement
Refinement on	F^2	F^2	F^2	F^2
R[F^2 > 2σ(F^2)], wR(F^2), S	0.043, 0.110, 0.75	0.055, 0.160, 1.03	0.056, 0.111, 1.07	0.083, 0.251, 0.94
No. of reflections	2843	710	1956	461
No. of parameters	151	61	125	62
H-atom treatment	Mixture of independent and constrained refinement	Not refined	Mixture of independent and constrained refinement	Not refined
Weighting scheme	w = 1/[σ^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)sin θ]; P(i) are: 0.700E^−1, 0.890, 0.00, 0.00, 0.00, 0.333	w = 1/[σ^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)sin θ]; P(i) are: 0.625E^−1, 1.91, 0.00, 0.00, 0.00, 0.333	w = 1/[σ^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)sin θ]; P(i) are: 0.172E^−1, 1.34, 0.00, 0.00, 0.00, 0.333	w = 1/[σ^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)sin θ]; P(i) are: 0.173, 0.00, 0.00, 0.00, 0.00, 0.333
(Δ/σ)max	0.001	0.007	<0.0001	0.001
Δρmax, Δρmin (e Å^−3)	0.44, −0.44	0.21, −0.20	0.32, −0.40	0.27, −0.20
Extinction method	None	None	Larson (1970)	None
Extinction coefficient	–	–	29 (9)	–

A new crystal was grown as above and then maintained at high temperature during data collection with the variable-temperature device set at 403 K. This is a nominal temperature, as there was presumably a significant temperature gradient across the cell as a whole, although across the sample itself the variation in temperature would have been small. The high-temperature dataset indexed on a slightly smaller orthorhombic unit cell with the following dimensions: a = 5.7168 (7), b = 9.9997 (19), c = 17.868 (2) Å. Both the b and c axes show a large change in length compared with the ambient temperature/0.36 GPa cell given above (Δb = +0.95 Å; Δc = −1.41 Å). This cell is also different from that obtained at low temperature (Table 1).

Conventional direct methods applied to the 403 K data set failed to yield a recognisable solution. This is a recurrent problem in high-pressure crystallography and is the result of low data-completeness. The problem can be overcome by using global optimization methods, originally devised for structure solution from powders. The crystal structure of 2-fluorophenol at high pressure was therefore solved using the simulated annealing procedure in the program DASH (David et al., 2001). The refinement of the structure followed the procedures outlined in §2.5.

2.7. Recovery of 4-chlorophenol grown at high pressure

The high melting point of 4-chlorophenol allowed the crystals of phase II formed at high pressure to be recovered without the sample melting. On release of the pressure the sample remained as a single crystal with a slight reduction in size due to melting around the edges. Diffraction data were collected at ambient pressure and 293 K, which showed the crystal to be 4-chlorophenol Phase I (see Table 1).

2.8. Software and other general procedures

A consistent numbering scheme was used for all the structures described here and this is shown in (I). Where there is

more than one molecule in the asymmetric unit the labels are augmented with the numbers 1, 2 etc. A full listing of crystal, data collection and refinement parameters is given in Table 1, and a set of hydrogen-bonding parameters is given in Table 2. The structures were visualized using SHELXTL (Sheldrick, 2001), MERCURY (Bruno et al., 2002) or CAMERON (Watkin et al., 1993); the figures were produced using DIAMOND (Crystal Impact, 2004). Other analyses utilized the p.c. version of PLATON (Spek, 2002; Farrugia, 1999). Searches of the Cambridge Structural Database (Allen, 2002; Allen & Motherwell, 2002) were carried out with the program CONQUEST, utilizing Version 5.25 of the database. Calculations involving projected vectors followed the methods of Sands (1995). Crystallographic information files for all structures reported here are available as supplementary material.¹

Table 2
Hydrogen-bonding parameters (Å)

The hydrogen-bonding distances are from donor to acceptor due to the imprecise determination of H-atom positions. H⋯Cl and H⋯F distances are given before and after the normalization of C—H distances to typical neutron values (1.083 Å), the latter being given in square brackets. The high-pressure crystal structure of 2-fluorophenol was determined at 403 K.

			D⋯A distance (Å)
Compound	Donor	Acceptor	Low-temperature (150 K)	High pressure
3-F	O7	O7^i	2.819 (1)	2.843 (8)
	H6	F8^ii	2.61 [2.48]	2.62 [2.49]
3-Cl	O71	O72^iii	2.734 (7)	2.693 (4)
	O72	O71	2.700 (6)	2.753 (4)
4-Cl phase I	O71	O72^iv	2.767 (2)	–
	O72	O71	2.779 (2)	–
	H62	Cl81^v	2.93 [2.82]	–
	H21	Cl82^vi	2.93 [2.82]	–
4-Cl phase II	O71	O72	2.762 (2)	2.819 (5)
	O72	O71^vii	2.779 (2)	2.749 (5)
	H31	Cl82^viii	2.83 [2.73]	2.85 [2.75]
2-F phase I	O71	O71^ix	2.774 (3)	–
	O71	O72	2.707 (2)	–
	O71	F81	2.690 (2)	–
	O71	F81^ix	2.942 (2)	–
2-F phase II	O71	O72^x	–	2.861 (7)
	O72	O71		3.097 (8)
	F81	H62^xi		2.56 [2.46]
	F82	H61^xii		2.56 [2.49]
	F82	H52^xiii		2.63 [2.53]
	O71	F82		2.941(7)
Symmetry codes: (i) ; (ii) 1+x, 1+y, z; (iii) ; (iv) ; (v) ; (vi) 1+x, y, z; (vii) 2-x, 1-y, 1-z; (viii) 1-x, 2-y, 1-z; (ix) 1-x, -y, 1-z; (x) ; (xi) ; (xii) -1+x,y,z; (xiii) .

3. Results

3.1. 3-Fluorophenol

3-Fluorophenol crystallizes at 263 K in the space group P2₁ with one molecule in the asymmetric unit. Diffraction data were collected at 150 K. The molecules interact via ⋯OH⋯OH⋯ hydrogen bonds to form chains disposed about the crystallographic 2₁ screw axes, conforming to a C(2) graph set (Fig. 2a). This packing motif is more commonly associated with small alcohols and was quite unexpected. It appears that stabilization of this motif occurs through the formation of H6⋯F8 interactions (2.61 Å) between the chains (Fig. 2b). Taken on their own these C—H⋯F interactions form chains which run along the 〈110〉 directions. The OH⋯O hydrogen bond present in this system is slightly longer [O7⋯O7′ 2.819 (1) Å] than those present in the other systems described in this paper. In projection onto (010) each chain is surrounded by six others.

Figure 2 (a) Crystal structure of 3-fluorophenol at 150 K viewed down the a axis. 3-Fluorophenol crystallizes with one molecule in the asymmetric unit in the space group P21, thereby forming a chain motif adopted by smaller alcohols. (b) Close contacts formed between H6⋯F8 of different chains (these contacts are omitted in Fig. 2a for clarity). Colour scheme: C black, F sea green, H light turquoise, O red.

The same phase is obtained on crystallization at 0.12 GPa. Neither the hydrogen bond nor the stabilizing C—H⋯F interaction are significantly different to those in the low-temperature structure [O7⋯O7′ 2.843 (8) Å; H6⋯F8 2.62 Å].

3.2. 3-Chlorophenol

3-Chlorophenol is a liquid under ambient pressure with a melting point of 306 K. At 283 K it crystallizes in space group P2₁2₁2₁ with two molecules in the asymmetric unit; diffraction data were collected at 150 K. Primary bond distances and angles are normal, and are available as supplementary material . The molecules interact via ⋯OH⋯OH⋯ hydrogen bonds to form pseudo-fourfold helical chains (Fig. 3a). The two crystallographically independent molecules alternate along the chains. The angle between successive C11—O71 and C12—O72 vectors in the chain when projected onto the (100) plane is 89.75°; in a perfect fourfold helix this value would be 90°. While the departure from projected fourfold symmetry in the OH⋯OH⋯ interaction is slight, the orientations of the chloro groups do not conform to the pseudo-symmetry – the angle between Cl–C vectors projected onto (100) is 17.74°. In addition, the molecules are not regularly spaced along the helix; the separations between the O atoms in the a direction are 0.44 or 1.55 Å (Fig. 3b).

Figure 3 (a) Crystal structure of 3-chlorophenol at 150 K. Distorted pseudo-fourfold helices are formed through OH⋯OH hydrogen bonds between the two molecules in the asymmetric unit. The structure at high pressure (0.1 GPa) is similar to the low-temperature structure. (b) Although in projection on (100), the positions of the C—O bonds resemble those in a fourfold helix and the positions of the molecules along the axis of the helix are irregular. Colour scheme as in Fig. 1.

The chains conform to a C₂²(4) graph set and are disposed about the 2₁ axes parallel to the a-axis direction (Fig. 3a). The two crystallographically independent hydrogen bonds are moderate in strength: O71⋯O72 2.734 (7) and O72⋯O71 2.700 (6) Å (Table 2). The chains appear to be close-packed when viewed in projection onto (100) and, in contrast to the fluoro derivative, there are no contacts between the chains that fall within the sums of the van der Waals radii.

Crystallization at 0.1 GPa results in the same structure as that at ambient pressure. The interactions between molecules are significantly different to those at ambient pressure [O71⋯O72 2.693 (4), O72⋯O71 2.753 (4) Å]. The interaction between O71⋯O72 appears to decrease in length at pressure while O72⋯O71 increases, although it is not possible to differentiate between the effects of pressure and temperature since the ambient pressure structure was determined at 150 K, while the high-pressure determination was at room temperature.

3.3. 4-Chlorophenol phase I at 150 K

4-Chlorophenol is a solid at room temperature and was characterized by Perrin & Michel (1973a, b). It crystallizes in two polymorphic forms and the structures of these have been redetermined at 150 K as part of this study.

Phase I crystallizes from the melt at ambient pressure in the space group P2₁/c with two molecules in the asymmetric unit; it is the more stable of the two phases. The two independent molecules alternate along the c direction, forming OH⋯OH⋯ hydrogen bonds resulting in a C₂²(4) graph set (Fig. 4a). The hydrogen bonds formed in this structure are of similar length: O71⋯O72 2.767 (2) and O72⋯O71 2.779 (2) Å.

Figure 4 (a) Crystal structure of phase I of 4-chlorophenol at 150 K viewed along the b axis, showing chains of molecules linked by OH⋯OH hydrogen bonds. (b) View down [001], along the chains. The Cl⋯H interactions occur between Cl82⋯H21 and Cl81⋯H62; the latter lie parallel to the b axis and run into the page. Colour scheme as in Fig. 1.

The graph-set descriptor is the same as that in 3-chloro­phenol, but the chain is built by successive application of c-glide operations rather than a screw axis. Although the chain is helical, with a repeat at every fourth molecule, the pseudo-fourfold symmetry is even less ideal than in 3-chlorophenol (Fig. 4b). The angle between O71—C11 and O72—C12 when projected onto (010) is 133.17°, which compares with 89.75° in 3-chlorophenol. Moreover, the spacing of molecules along the direction of the helix is irregular: the spacings of the O atoms in the c direction are 1.98 and 2.39 Å.

The chains are linked by H21⋯Cl82 and H62⋯Cl81 interactions, both measuring 2.93 Å (Fig. 4b). Taken on their own these C—Cl⋯H interactions build spiral chains which are disposed about the 2₁ axis parallel to b. Neighbouring chains interact with one another through a π-stacking interaction between pairs of symmetry-equivalent molecules containing C11—Cl81. The distance between the phenyl ring planes is 3.45 Å with the centroids separated by 3.77 Å, which equates to a 1.74 Å centroid displacement.

3.4. 4-Chlorophenol phase II at 150 K and 0.02 GPa

The second phase of 4-chlorophenol is obtained by recrystallization from benzene; it is in the same space group as phase I, P2₁/c, with two molecules in the asymmetric unit. Phase II is metastable and transforms spontaneously to phase I if placed in contact with it (Perrin & Michel, 1973b).

As in phase I, the molecules interact via ⋯OH⋯OH⋯ hydrogen bonds, but the interactions form an R₄⁴(8) graph set rather than hydrogen-bonded chains (Fig. 5). These rings stack along the a direction. The hydrogen bonds are of a similar length to those in phase I; O71⋯O72 2.762 (2) and O72⋯O71 2.779 (2) Å. Within the R₄⁴(8) rings a secondary CH⋯π interaction is formed between H21 and the π-system of molecule 2 (comprising atoms C12–C62). The H21⋯ π-centroid is 3.95 Å, near to the limit for these interactions (4 Å) as defined by Malone et al. (1997), and it adopts a `Type V' motif, as defined by the same authors.

Figure 5 Crystal structure of phase II of 4-chlorophenol at 150 K viewed along the a axis. The molecules crystallize in a ring motif that forms around an approximate fourfold axis. The discrete hydrogen-bonded groups are linked through an interaction between Cl82⋯H31. The structure at high pressure is similar to the low-temperature structure. Colour scheme as in Fig. 1.

There are close contacts between Cl and H atoms (Cl82⋯H31 2.83 Å cf. sum of van der Waals' 2.95 Å) that join the R₄⁴(8) groups together into a ribbon. The ribbons lie along the [110] direction at c = ½ and the [10] direction at c = 0, 1 etc.

Under ambient conditions crystallization of 4-chlorophenol from the melt yields phase I, but when crystallized from the melt under pressure (0.02 GPa), phase II is formed. This pressure is very slight indeed by the standards of high-pressure crystallography and is barely measurable using the ruby fluorescence technique. The molecular arrangement is the same as the ambient pressure structure, although O71⋯O72 is significantly longer than at ambient pressure [2.819 (5) Å], while O72⋯O71 is significantly shorter [2.749 (5) Å]. A similar effect was observed in 3-chlorophenol.

The crystal of phase II grown at high pressure transformed to a single crystal of phase I when the pressure was released, but this transformation is not reversible, i.e. applying hydrostatic pressure to a crystal of phase I does not yield phase II. It is possible that the phase II-to-I transformation occurs by conversion of the R₄⁴(8) ring motifs, which are stacked by lattice repeats along the a direction in phase I, into C₄⁴(8) chains, developed by a c glide, in phase II. Such a change in the intermolecular interactions would approximately double the length of the lattice repeat in the a direction in going from phase I to II (a = 3.97 and c = 8.74 Å in phases I and II, respectively). In both phases C—Cl⋯H interactions build chains which spiral along the 2₁-axes along the b directions. These similarities presumably promote the preservation of the single crystal through the phase transition.

3.5. 2-Fluorophenol phase I at 150 K

2-Fluorophenol crystallizes in space group C2/c with one-and-a-half molecules in the asymmetric unit. We refer to this phase as phase I. One molecule (molecule 1, C11–F81) occupies a general position and is ordered. A second molecule (molecule 2, C12–F82) occupies a twofold axis with the axis running through atoms O72⋯C12⋯C42, and so the hydroxyl hydrogen and the F atoms are disordered.

The molecules interact via ⋯OH⋯OH⋯ hydrogen bonds forming chains; the direction of the hydrogen bonding in these chains must be disordered as a result of the disorder in molecule 2. A pair of molecules of type 1 are connected by a hydrogen bond formed across an inversion centre. These `dimer' sub-units are then bridged by disordered molecules of type 2 (Fig. 6a). When projected along a the chains have a marked zigzag structure. When viewed in projection along c the chain of molecules somewhat resembles a helix, but the resemblance is an artefact of the projection: the displacement along c of one molecule to another is quite irregular, being 2.18 Å across the inversion centre and 5.75 Å across the twofold axis, while the angles made between successive OC vectors alternate between 180 and 89.83° (Fig. 6b). The hydrogen-bond lengths are similar to those observed for other compounds in the study: O71⋯O71 2.774 (3) and O71⋯O72 2.707 (2) Å. There are π-stacking interactions between molecule 1 and a symmetry equivalent in the next chain along the a axis. The phenyl rings lie parallel to one another 3.62 Å apart with a centroid displacement in the plane of the ring of 1.48 Å.

Figure 6 (a) Crystal structure of phase I of 2-fluorophenol at 150 K showing the disordered hydrogen-bonded chain. Molecule 1 forms a dimer with a symmetry-equivalent molecule. These dimers are linked through a hydrogen-bonding interaction to molecule 2. H atoms are omitted for clarity. F82 is disordered by the twofold axis which runs through O72—C12. (b) View down the hydrogen-bonded chain. Colour scheme as in Fig. 2.

3.6. 2-Fluorophenol phase II at 0.36 GPa and 403 K

A crystal of 2-fluorophenol was grown at 0.36 GPa, but the crystal fractured a few hours after cooling to ambient temperature. Despite the poor X-ray diffraction data, the diffraction pattern could be indexed on an orthorhombic unit cell (a = 5.8952, b = 10.9466, c = 16.459 Å); this is different to that determined at ambient pressure at 150 K, indicating that a different phase had formed under high pressure. A tentative structural solution was obtained, but the refinement residuals were unacceptably high and it is likely that on cooling to room temperature the compound forms a disordered phase.

We found that the crystal obtained at high pressure was stable if the cell was held above ca 363 K and so a data collection was carried out in which the cell was held at 403 K. This phase of 2-fluorophenol crystallizes in the space group P2₁2₁2₁ with two molecules in the asymmetric unit. In one molecule the C—F bond refined to an unrealistically short distance, which may indicate high librational disorder of the molecule. This is not unreasonable for a structure at 403 K, although it is difficult to assess from the displacement parameters because of the low data completeness which resulted from shading by the pressure cell.

Oxygen and fluorine have similar X-ray scattering factors and so assignment of these sites was made on the basis of interatomic contacts. The assumption that O atoms are likely to make at least one hydrogen bond in which the distance between the non-H atoms is between 2.6 and 3.1 Å serves to identify O71 as an oxygen atom. The shortest contact (3.37 Å) made by F81 is to C62 in a neighbouring ring; this distance is similar to those quoted by Thalladi et al. (1998) for C⋯F distances in C—H⋯F hydrogen bonds, which therefore lends support to the assignment.

Atom assignments, O72 and F82, in the second of the two independent molecules were made by the refinement of two alternative models with part-weight hydroxyl H atoms placed in two alternative positions on each O atom. The R1 factors for the model presented here and the alternative were 0.121 and 0.124, respectively. The occupancies of alternative H-atom positions refined to 0.85:0.15 (13); only the H atoms of major occupancy were retained. The alternative model contains OH⋯F interactions; organic fluorine is not expected to be competitive with hydroxyl oxygen as a hydrogen-bond acceptor.

The OH⋯OH⋯ chain that is formed (along the a direction) conforms to a C₂²(4) graph set. The O71⋯O72 distances are 2.861 (7) and 3.097 (8) Å. In common with other structures in this series, each chain is surrounded by six others and there are F82⋯H52 interactions formed between the chains (2.63 Å, Fig. 7a). The O⋯O distance of 3.097 (8) Å is the longest observed for an OH⋯OH interaction in this series and the length of the interaction may reflect the steric effect of F72 [O71⋯F72 2.941 (7) Å]. This arrangement is stabilized by secondary F81⋯H62 and F82⋯F61 interactions (both 2.56 Å) formed within the chains (Fig. 7b).

Figure 7 (a) Crystal structure of phase II of 2-fluorophenol at 0.36 GPa viewed along a showing chains of molecules linked by OH⋯OH hydrogen bonds. The chains are linked by C—H⋯F hydrogen bonds between H52 and F82. (b) The hydrogen-bonded chains viewed side-on. Colour scheme as in Fig. 2.

4. Discussion

Compounds that are crystallized under ambient conditions and then subjected as single crystals to high pressure may be reduced to powder during a phase transition. Low-melting compounds are therefore useful for the study of pressure-induced polymorphism because high-pressure phases can be accessed directly by in situ crystallization in a high-pressure cell. A particularly striking example of the simplification in phase behaviour that can be gained by in situ crystallization is that of S₈: the solid-region temperature/pressure phase diagram contains no less than 12 different phases when studied by compression of a solid sample, but there are only three when the liquid is allowed to crystallize from the melt (Mezouar, 2001). The series of molecules reported herein was chosen for its well defined hydrogen-bonding characteristics and the rigidity of the molecules.

We have described the structures of 2-chlorophenol and 4-fluorophenol in a previous paper (Oswald et al., 2005) and the aim of this paper is to complete our survey of the monofluoro- and monochlorophenols.

The packing in the crystal structures of monoalcohols has been studied by Brock & Duncan (1994) and Taylor & Macrae (2001). Alcohols with bulky R groups aggregate around three-, four- or sixfold screw, rotation or rotoinversion axes or crystallize in low-symmetry space groups with Z′ > 1. Small alcohols tend to pack about 2₁ axes or glide planes. Our previous work has shown that phenol, 2-chlorophenol and 4-fluoro­phenol behave like bulky alcohols at low temperature (packing about a pseudo-threefold axis in P2₁, a 3₂ axis in P3₂ or a site in R, respectively), but behave as small alcohols, packing about 2₁ axes or glide planes, at high pressure.

3-Chlorophenol behaves typically, and packs with two independent molecules about a 2₁ axis to emulate a fourfold screw axis, although there are significant departures from this ideal arrangement. This structure is obtained both at low-temperature (283 K) and high pressure (0.1 GPa). The geometric parameters characterizing the packing were slightly different. All or most of the interactions would be expected to decrease in length on further application of pressure, but one disadvantage of the methods used here is that hydrostatic conditions are lost on crystallization under pressure (the liquid behaves as its own hydrostatic fluid). Increasing the pressure on such samples therefore tends to degrade them.

3-Fluorophenol is unique in this series of compounds in crystallizing at ambient pressure like a small alcohol and forming chains disposed about a 2₁ screw axis. The O⋯O distances in the chain are slightly longer than in the other phenols studied here and this may reflect steric effects in neighbouring phenyl groups. The structure is stabilized by F⋯H interactions. The same phase is obtained on crystallization at 0.12 GPa.

Both 2-fluorophenol and 4-chlorophenol exhibit more interesting phase behaviour with increasing pressure. Neither adopts the packing motif associated with small alcohols at high pressure; nor do they form very regular helical structures at ambient pressure.

The structure of 2-fluorophenol phase I at 150 K is depicted in Fig. 6. The packing is characterized by chains built by OH⋯OH⋯ hydrogen bonds. Pairs of molecules are linked across inversion centres; each pair is bridged by molecules disordered about twofold axes. The pairs of molecules connected across the inversion centres have a similar spatial relationship to a pair of molecules related by a glide plane or 2₁ axis, as in the structures of small alcohols. The steric effect of the 2-fluorine atom means that this relationship cannot be propagated further and the other molecules in the chain are rotated about the chain axis (the c direction) by ca 90°. The 2-fluorine atoms point towards the chain axis and there is no scope for the formation of stabilizing F⋯H contacts either within the chains or between them.

A different polymorph (phase II) was obtained for 2-fluorophenol at 0.36 GPa. The crystal of this phase was stable only above ca 363 K and data were obtained at 403 K. The structure has two molecules in the asymmetric unit and is also characterized by OH⋯OH⋯ chain formation. In projection the chain resembles a fourfold helix, but the repeat along the chain is irregular. The most important difference between this phase and phase I is the presence of F⋯H interactions which occur both within the hydrogen-bonded chains and between them. Thalladi et al. (1998) have shown that the C—H⋯F interactions are as important as C—H⋯O interactions in structure stabilization. The observation that more of these weak interactions are formed at high pressure is consistent with results observed in other high-pressure studies, for example, on glycine, where high-pressure induces extensive CH⋯O hydrogen-bond formation (Dawson et al., 2005). A feature exhibited by the high-pressure structures of 2-chlorophenol and 4-fluorophenol is the lengthening of OH⋯OH⋯ hydrogen bonds in order to accommodate more efficient packing motifs. A similar feature is observed in phase II of 2-fluorophenol, in which one O⋯O interaction is 3.097 (3) Å.

The two phases of 4-chlorophenol presented here have been described previously and these structures are redeterminations. Phase I, which is based on an irregular helical arrangement of molecules linked by OH⋯OH interactions, crystallizes at ambient pressure from the melt. Under a modest pressure of 0.02 GPa, crystallization from the melt yields phase II, which is based on cyclic hydrogen-bonded tetramers. In both phases the Cl atoms link the hydrogen-bonded units together through C—Cl⋯H interactions. These are somewhat shorter in phase II than in phase I. Moreover, the R⁴₄(8) ring has inversion symmetry rather than the symmetry that might be expected for such a motif for a bulky alcohol. Neighbouring phenyl groups approach each other with centroid–centroid distances of 6.22 Å, mediated by a CH⋯aryl hydrogen bond. The more extensive set of contacts in phase II and its more efficient packing of phenyl groups perhaps explains the preference for this phase at high pressure.

5. Conclusions

The behaviour of the 3-chloro, 3-fluoro-, 4-chloro- and 2-fluorophenol show a departure from the behaviour observed in phenol, 2-chlorophenol and 4-fluorophenol. The transition to a small alcohol packing from bulky alcohol packing is not seen in any of the former compounds. In general, we find that they crystallize in pseudo-helices and ring motifs, although these are markedly distorted from three- or fourfold symmetry often observed in alcohol structures. Only one compound, 2-fluorophenol, shows a phase that is only stable at high pressure. Those compounds that do undergo a phase transition, 4-chlorophenol and 2-fluorophenol, show a transition to a phase which possesses a greater number of weaker intermolecular contacts in the form of CH⋯π and C—H⋯F interactions, respectively.

Supporting information

S1. Comment

063_ALERT_3_B Crystal Probably too Large for Beam Size ······. 1.00 mm

This crystal was grown by laser (see text) in a capilliary. It was very difficult to the precise length of the crystal grown. Gorbitz has shown that use of a large crystal does not appear to affect data quality. See C. H. Gorbitz Acta Cryst. (1999). B55, 1090–1098

032_ALERT_4_C Std Uncertainty in Flack Parameter too High ···. 3.00 850_ALERT_2_C Check Flack Parameter Exact Value 0.00 and su.. 3.00

This crystal does not contain any elements that would contribute significantly to anomalous scattering therefore the Flack parameter is undetermined.

061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ············. 0.76

This long sample is inclined at 54 ° in chi and absorption will be quite significant as the sample passes beneath the collimator. Note that the capillary will contribute to the transmission factors also.

The glass caillary will contribute to the transmission factors also.

125_ALERT_4_C No _symmetry_space_group_name_Hall Given ······. ? 790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C6 H5 F O

Noted; no action taken.

Computing details

For all compounds, data collection: SMART (Siemens, 1993); cell refinement: SAINT (Siemens ,1995); data reduction: SAINT (Siemens ,1995). Program(s) used to solve structure: SHELXS 86 (Sheldrick, 1986) for (3F); SIR92 for 3FP; USER DEFINED STRUCTURE SOLUTION for 3CL, 3CLP, 4CL2P, 2F1; SIR92 (Altomare et al., 1994) for 4CL1, 4CL2; DASH for 2F2P. For all compounds, program(s) used to refine structure: CRYSTALS (Betteridge et al. 2003); molecular graphics: CAMERON (Watkin et al. 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al. 2003).

Figures

(3F)

Crystal data

C6H5FO	F(000) = 116
Mr = 112.10	Dx = 1.464 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 5.6510 (12) Å	Cell parameters from 711 reflections
b = 5.0642 (10) Å	θ = 2–28°
c = 9.3185 (19) Å	µ = 0.12 mm^−1
β = 107.518 (4)°	T = 150 K
V = 254.31 (9) Å^3	Cylinder, colourless
Z = 2	1.00 × 0.32 × 0.32 mm

Data collection

Bruker SMART diffractometer	608 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
ω scans	θmax = 28.6°, θmin = 2.3°
Absorption correction: multi-scan SADABS (Siemens, 1996)	h = −6→7
Tmin = 0.67, Tmax = 0.96	k = −6→6
1603 measured reflections	l = −12→9
672 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.037	P = P(6)*max(Fo^2,0) + (1-P(6))Fc^2 Method = SHELXL 97 (Sheldrick, 1997) W = 1. / [Sigma^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)Sin(theta)] P(i) are: 0.553E-01 0.625E-03 0.00 0.00 0.00 0.333
wR(F^2) = 0.092	(Δ/σ)max = 0.000153
S = 1.05	Δρmax = 0.22 e Å^−3
672 reflections	Δρmin = −0.22 e Å^−3
77 parameters	Absolute structure: Flack, 0 Friedel-pairs
1 restraint	Absolute structure parameter: 0 (3)
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.2972 (3)	−0.3568 (5)	−0.1685 (2)	0.0213
C2	−0.4652 (4)	−0.5476 (6)	−0.1529 (2)	0.0246
C3	−0.6955 (3)	−0.5503 (5)	−0.2601 (2)	0.0247
C4	−0.7650 (3)	−0.3756 (6)	−0.3785 (2)	0.0275
C5	−0.5942 (4)	−0.1887 (6)	−0.3904 (2)	0.0281
C6	−0.3595 (4)	−0.1777 (5)	−0.2865 (2)	0.0247
O7	−0.0640 (3)	−0.3371 (4)	−0.06698 (18)	0.0289
F8	−0.8607 (2)	−0.7366 (7)	−0.24734 (16)	0.0374
H7	−0.026 (7)	−0.469 (9)	−0.023 (4)	0.0500*
H2	−0.4233	−0.6705	−0.0721	0.0299*
H4	−0.9254	−0.3834	−0.4498	0.0314*
H5	−0.6378	−0.0656	−0.4710	0.0326*
H6	−0.2429	−0.0491	−0.2962	0.0298*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0213 (9)	0.0191 (11)	0.0226 (9)	0.0032 (10)	0.0051 (8)	−0.0047 (10)
C2	0.0297 (10)	0.0202 (11)	0.0245 (10)	0.0009 (9)	0.0093 (8)	0.0011 (9)
C3	0.0234 (9)	0.0207 (11)	0.0327 (12)	−0.0048 (10)	0.0123 (9)	−0.0078 (11)
C4	0.0188 (8)	0.0293 (13)	0.0301 (10)	0.0018 (10)	0.0010 (8)	−0.0045 (11)
C5	0.0281 (10)	0.0255 (13)	0.0276 (11)	0.0052 (11)	0.0039 (9)	0.0031 (10)
C6	0.0249 (9)	0.0181 (12)	0.0310 (11)	−0.0025 (9)	0.0083 (9)	−0.0011 (9)
O7	0.0262 (7)	0.0242 (9)	0.0287 (8)	−0.0021 (7)	−0.0033 (6)	−0.0002 (8)
F8	0.0334 (7)	0.0313 (8)	0.0488 (8)	−0.0138 (6)	0.0146 (6)	−0.0047 (7)

Geometric parameters (Å, º)

C1—C2	1.392 (3)	C4—C5	1.380 (3)
C1—C6	1.387 (3)	C4—H4	0.950
C1—O7	1.375 (2)	C5—C6	1.388 (3)
C2—C3	1.382 (3)	C5—H5	0.950
C2—H2	0.950	C6—H6	0.950
C3—C4	1.376 (3)	O7—H7	0.78 (4)
C3—F8	1.358 (4)
C2—C1—C6	121.21 (17)	C3—C4—H4	121.073
C2—C1—O7	121.4 (2)	C5—C4—H4	121.061
C6—C1—O7	117.4 (2)	C4—C5—C6	121.1 (2)
C1—C2—C3	117.1 (2)	C4—C5—H5	119.489
C1—C2—H2	121.456	C6—C5—H5	119.422
C3—C2—H2	121.493	C5—C6—C1	119.22 (19)
C2—C3—C4	123.56 (19)	C5—C6—H6	120.390
C2—C3—F8	117.8 (2)	C1—C6—H6	120.387
C4—C3—F8	118.65 (19)	C1—O7—H7	111 (3)
C3—C4—C5	117.87 (18)

(3FP)

Crystal data

C6H5FO	F(000) = 116
Mr = 112.10	Dx = 1.433 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 5.6747 (9) Å	Cell parameters from 398 reflections
b = 5.0760 (4) Å	θ = 5–23°
c = 9.4753 (13) Å	µ = 0.12 mm^−1
β = 107.832 (11)°	T = 293 K
V = 259.82 (6) Å^3	Blocks, colourless
Z = 2	0.30 × 0.30 × 0.18 mm

Data collection

Bruker SMART diffractometer	146 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ω scans	θmax = 23.2°, θmin = 4.5°
Absorption correction: multi-scan SADABS (Siemens, 1996)	h = −1→2
Tmin = 0.67, Tmax = 0.98	k = −5→0
1310 measured reflections	l = −10→0
159 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.064	P = P(6)*max(Fo^2,0) + (1-P(6))Fc^2 Method = SHELXL 97 (Sheldrick, 1997) W = 1. / [Sigma^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)Sin(theta)] P(i) are: 0.694E-01 0.349 0.00 0.00 0.00 0.333
wR(F^2) = 0.160	(Δ/σ)max = 0.000023
S = 1.15	Δρmax = 0.17 e Å^−3
159 reflections	Δρmin = −0.16 e Å^−3
32 parameters	Absolute structure: Flack, 0 Friedel-pairs
15 restraints	Absolute structure parameter: −11 (7)
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O7	−0.070 (3)	−0.3345 (11)	−0.0673 (7)	0.0611
F8	−0.863 (3)	−0.7372 (9)	−0.2468 (6)	0.0734
H7	−0.0252	−0.4643	−0.0249	0.0500*
C1	−0.2985	−0.3541	−0.1672	0.041 (2)*
C2	−0.4681	−0.5424	−0.1537	0.050 (3)*
C3	−0.7010	−0.5549	−0.2585	0.058 (3)*
C4	−0.7642	−0.3793	−0.3766	0.059 (3)*
C5	−0.5946	−0.1910	−0.3901	0.054 (3)*
C6	−0.3617	−0.1784	−0.2854	0.050 (3)*
H2	−0.4250	−0.6624	−0.0730	0.0603*
H4	−0.9234	−0.3879	−0.4482	0.0706*
H5	−0.6377	−0.0709	−0.4709	0.0641*
H6	−0.2457	−0.0497	−0.2946	0.0596*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O7	0.05 (3)	0.053 (4)	0.060 (3)	−0.003 (7)	−0.011 (6)	0.000 (3)
F8	0.06 (3)	0.062 (4)	0.104 (5)	−0.025 (7)	0.030 (7)	−0.005 (3)

Geometric parameters (Å, º)

O7—H7	0.773	C3—C4	1.39
O7—C1	1.354 (15)	C4—C5	1.39
F8—C3	1.331 (12)	C4—H4	0.950
C1—C2	1.39	C5—C6	1.39
C1—C6	1.39	C5—H5	0.950
C2—C3	1.39	C6—H6	0.950
C2—H2	0.950
H7—O7—C1	113.192	C3—C4—C5	120.00
O7—C1—C2	121.9 (3)	C3—C4—H4	120.000
O7—C1—C6	118.1 (3)	C5—C4—H4	120.000
C2—C1—C6	120.00	C4—C5—C6	120.00
C1—C2—C3	120.00	C4—C5—H5	120.000
C1—C2—H2	120.000	C6—C5—H5	120.000
C3—C2—H2	120.000	C5—C6—C1	120.00
C2—C3—F8	120.1 (4)	C5—C6—H6	120.000
C2—C3—C4	120.00	C1—C6—H6	120.000
F8—C3—C4	119.9 (4)

(3CL)

Crystal data

C6H5ClO	Dx = 1.487 Mg m^−3
Mr = 128.56	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 1504 reflections
a = 3.9846 (5) Å	θ = 5–25°
b = 13.9272 (19) Å	µ = 0.55 mm^−1
c = 20.699 (3) Å	T = 150 K
V = 1148.7 (3) Å^3	Rod, colourless
Z = 8	0.90 × 0.10 × 0.10 mm
F(000) = 528

Data collection

Bruker SMART diffractometer	1376 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan SADABS (Siemens, 1996)	h = −4→4
Tmin = 0.22, Tmax = 0.95	k = −16→15
4548 measured reflections	l = −24→22
1987 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.069	P = P(6)*max(Fo^2,0) + (1-P(6))Fc^2 Method = SHELXL 97 (Sheldrick, 1997) W = 1. / [Sigma^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)Sin(theta)] P(i) are: 0.00 0.00 0.00 0.00 0.00 0.333
wR(F^2) = 0.143	(Δ/σ)max = 0.000204
S = 0.94	Δρmax = 0.56 e Å^−3
1977 reflections	Δρmin = −0.58 e Å^−3
152 parameters	Absolute structure: Flack, 10 Friedel-pairs
2 restraints	Absolute structure parameter: 0.1 (2)
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C11	0.1389 (17)	−0.4542 (5)	−1.0155 (3)	0.0307
C21	0.2721 (18)	−0.5022 (5)	−0.9628 (3)	0.0298
C31	0.4339 (17)	−0.5888 (4)	−0.9724 (3)	0.0285
C41	0.4796 (19)	−0.6256 (5)	−1.0352 (3)	0.0354
C51	0.3484 (18)	−0.5759 (5)	−1.0870 (4)	0.0390
C61	0.1842 (17)	−0.4893 (5)	−1.0775 (3)	0.0292
O71	−0.0253 (14)	−0.3688 (3)	−1.0033 (2)	0.0380
Cl81	0.5944 (5)	−0.64964 (14)	−0.90659 (9)	0.0436
C12	−0.0342 (18)	−0.2531 (5)	−0.8518 (3)	0.0299
C22	−0.1901 (16)	−0.3385 (5)	−0.8375 (3)	0.0264
C32	−0.3016 (15)	−0.3544 (5)	−0.7756 (3)	0.0339
C42	−0.2603 (17)	−0.2870 (5)	−0.7263 (3)	0.0348
C52	−0.1052 (17)	−0.2016 (5)	−0.7422 (3)	0.0351
C62	0.0089 (19)	−0.1837 (4)	−0.8041 (3)	0.0344
O72	0.0864 (14)	−0.2336 (3)	−0.9123 (2)	0.0385
Cl82	−0.4871 (5)	−0.46531 (12)	−0.75731 (8)	0.0423
H72	0.02 (2)	−0.277 (4)	−0.935 (3)	0.0500*
H71	−0.08 (2)	−0.351 (5)	−1.043 (2)	0.0500*
H21	0.2523	−0.4760	−0.9206	0.0358*
H41	0.5991	−0.6838	−1.0417	0.0425*
H51	0.3707	−0.6011	−1.1294	0.0468*
H61	0.1026	−0.4541	−1.1135	0.0351*
H22	−0.2204	−0.3859	−0.8699	0.0316*
H42	−0.3358	−0.2995	−0.6836	0.0418*
H52	−0.0762	−0.1539	−0.7098	0.0421*
H62	0.1159	−0.1246	−0.8140	0.0413*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C11	0.030 (4)	0.026 (4)	0.036 (4)	−0.009 (3)	0.003 (3)	0.002 (3)
C21	0.026 (4)	0.037 (4)	0.026 (4)	−0.006 (3)	−0.001 (3)	−0.002 (3)
C31	0.021 (4)	0.019 (3)	0.045 (4)	−0.008 (3)	−0.001 (3)	0.002 (3)
C41	0.025 (4)	0.032 (4)	0.049 (4)	0.000 (3)	0.001 (4)	−0.006 (3)
C51	0.035 (4)	0.041 (4)	0.042 (4)	0.000 (3)	0.003 (4)	−0.014 (4)
C61	0.037 (4)	0.024 (4)	0.026 (4)	−0.006 (3)	0.000 (3)	0.005 (3)
O71	0.046 (3)	0.029 (3)	0.039 (3)	0.003 (3)	−0.010 (3)	−0.001 (2)
Cl81	0.0423 (11)	0.0392 (10)	0.0493 (10)	0.0064 (9)	0.0005 (10)	0.0103 (9)
C12	0.027 (4)	0.033 (4)	0.030 (3)	0.004 (3)	−0.002 (3)	0.004 (3)
C22	0.033 (4)	0.015 (3)	0.031 (3)	0.004 (3)	−0.001 (3)	0.001 (3)
C32	0.020 (3)	0.035 (4)	0.046 (4)	0.009 (3)	0.002 (3)	0.014 (4)
C42	0.032 (4)	0.042 (4)	0.030 (4)	0.007 (4)	0.000 (3)	0.002 (3)
C52	0.034 (4)	0.036 (4)	0.036 (4)	0.005 (3)	−0.005 (4)	−0.005 (3)
C62	0.035 (4)	0.026 (3)	0.042 (4)	−0.005 (3)	−0.003 (4)	0.002 (3)
O72	0.052 (3)	0.032 (3)	0.032 (3)	−0.010 (3)	0.004 (3)	0.001 (2)
Cl82	0.0432 (10)	0.0337 (9)	0.0500 (10)	−0.0004 (9)	0.0075 (10)	0.0070 (8)

Geometric parameters (Å, º)

C11—C21	1.387 (9)	C12—C22	1.374 (9)
C11—C61	1.384 (8)	C12—C62	1.393 (8)
C11—O71	1.381 (8)	C12—O72	1.368 (7)
C21—C31	1.382 (9)	C22—C32	1.373 (8)
C21—H21	0.950	C22—H22	0.950
C31—C41	1.409 (8)	C32—C42	1.396 (9)
C31—Cl81	1.727 (7)	C32—Cl82	1.754 (7)
C41—C51	1.380 (10)	C42—C52	1.381 (9)
C41—H41	0.950	C42—H42	0.950
C51—C61	1.385 (9)	C52—C62	1.382 (9)
C51—H51	0.950	C52—H52	0.950
C61—H61	0.950	C62—H62	0.950
O71—H71	0.89 (4)	O72—H72	0.81 (4)
C21—C11—C61	120.6 (7)	C22—C12—C62	120.2 (6)
C21—C11—O71	116.9 (6)	C22—C12—O72	121.9 (6)
C61—C11—O71	122.4 (6)	C62—C12—O72	117.9 (6)
C11—C21—C31	119.0 (6)	C12—C22—C32	119.1 (6)
C11—C21—H21	120.476	C12—C22—H22	120.427
C31—C21—H21	120.475	C32—C22—H22	120.427
C21—C31—C41	120.8 (6)	C22—C32—C42	122.4 (6)
C21—C31—Cl81	119.1 (5)	C22—C32—Cl82	118.6 (6)
C41—C31—Cl81	120.1 (5)	C42—C32—Cl82	118.9 (5)
C31—C41—C51	119.0 (7)	C32—C42—C52	117.3 (6)
C31—C41—H41	120.481	C32—C42—H42	121.369
C51—C41—H41	120.486	C52—C42—H42	121.368
C41—C51—C61	120.3 (7)	C42—C52—C62	121.5 (6)
C41—C51—H51	119.827	C42—C52—H52	119.250
C61—C51—H51	119.827	C62—C52—H52	119.249
C51—C61—C11	120.0 (6)	C12—C62—C52	119.5 (6)
C51—C61—H61	119.981	C12—C62—H62	120.240
C11—C61—H61	119.981	C52—C62—H62	120.235
C11—O71—H71	101 (5)	C12—O72—H72	105 (5)

(3CLP)

Crystal data

C6H5ClO	Dx = 1.451 Mg m^−3
Mr = 128.56	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 983 reflections
a = 4.0949 (4) Å	θ = 3–23°
b = 13.875 (3) Å	µ = 0.53 mm^−1
c = 20.716 (3) Å	T = 293 K
V = 1177.0 (3) Å^3	Colourless, block
Z = 8	0.30 × 0.30 × 0.18 mm
F(000) = 528

Data collection

Bruker SMART diffractometer	476 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.147
ω scans	θmax = 23.3°, θmin = 2.5°
Absorption correction: multi-scan SADABS (Siemens, 1996)	h = 0→4
Tmin = 0.85, Tmax = 0.91	k = 0→13
6533 measured reflections	l = 0→21
780 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.098	P = P(6)*max(Fo^2,0) + (1-P(6))Fc^2 Method = SHELXL 97 (Sheldrick, 1997) W = 1. / [Sigma^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)Sin(theta)] P(i) are: 0.106 5.04 0.00 0.00 0.00 0.333
wR(F^2) = 0.244	(Δ/σ)max = 0.004
S = 0.99	Δρmax = 0.59 e Å^−3
780 reflections	Δρmin = −0.56 e Å^−3
62 parameters	Absolute structure: Flack, 0 Friedel-pairs
64 restraints	Absolute structure parameter: 1.1 (5)
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C11	0.1433	−0.4528	−1.0157	0.043 (4)*
C21	0.2743	−0.5021	−0.9634	0.047 (4)*
C31	0.4446	−0.5875	−0.9732	0.054 (4)*
C41	0.4839	−0.6236	−1.0353	0.064 (4)*
C51	0.3529	−0.5743	−1.0876	0.058 (4)*
C61	0.1826	−0.4888	−1.0778	0.050 (4)*
O71	−0.026 (2)	−0.3696 (2)	−1.00767 (10)	0.0683
Cl81	0.5969 (11)	−0.6480 (2)	−0.90755 (14)	0.0800
C12	−0.0220	−0.2536	−0.8523	0.049 (4)*
C22	−0.1816	−0.3392	−0.8375	0.053 (4)*
C32	−0.2985	−0.3550	−0.7754	0.054 (4)*
C42	−0.2557	−0.2852	−0.7281	0.061 (4)*
C52	−0.0960	−0.1995	−0.7428	0.066 (5)*
C62	0.0208	−0.1838	−0.8049	0.061 (4)*
O72	0.1012 (16)	−0.2366 (3)	−0.9123 (2)	0.0641
Cl82	−0.4850 (11)	−0.4630 (3)	−0.75811 (10)	0.0773
H71	−0.1478	−0.3540	−1.0393	0.0500*
H72	0.0260	−0.2718	−0.9414	0.0500*
H21	0.2475	−0.4775	−0.9209	0.0562*
H41	0.6003	−0.6820	−1.0420	0.0762*
H51	0.3797	−0.5989	−1.1301	0.0703*
H61	0.0930	−0.4551	−1.1136	0.0610*
H22	−0.2109	−0.3870	−0.8699	0.0630*
H42	−0.3356	−0.2959	−0.6856	0.0724*
H52	−0.0668	−0.1518	−0.7105	0.0798*
H62	0.1299	−0.1252	−0.8150	0.0731*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O71	0.087 (7)	0.060 (10)	0.059 (7)	0.020 (7)	−0.015 (6)	−0.006 (4)
Cl81	0.104 (3)	0.061 (4)	0.074 (3)	0.013 (3)	0.003 (3)	0.024 (2)
O72	0.108 (8)	0.038 (9)	0.047 (6)	−0.018 (6)	0.016 (6)	−0.005 (4)
Cl82	0.099 (3)	0.060 (4)	0.073 (3)	0.003 (3)	0.018 (3)	0.0178 (19)

Geometric parameters (Å, º)

C11—C21	1.39	C12—C22	1.39
C11—C61	1.39	C12—C62	1.39
C11—O71	1.356 (4)	C12—O72	1.361 (3)
C21—C31	1.39	C22—C32	1.39
C21—H21	0.950	C22—H22	0.950
C31—C41	1.39	C32—C42	1.39
C31—Cl81	1.715 (4)	C32—Cl82	1.719 (4)
C41—C51	1.39	C42—C52	1.39
C41—H41	0.950	C42—H42	0.950
C51—C61	1.39	C52—C62	1.39
C51—H51	0.950	C52—H52	0.950
C61—H61	0.950	C62—H62	0.950
O71—H71	0.852	O72—H72	0.834
C21—C11—C61	120.00	C22—C12—C62	120.00
C21—C11—O71	121.37 (7)	C22—C12—O72	121.51 (7)
C61—C11—O71	118.63 (7)	C62—C12—O72	118.48 (6)
C11—C21—C31	120.00	C12—C22—C32	120.00
C11—C21—H21	120.000	C12—C22—H22	120.000
C31—C21—H21	120.000	C32—C22—H22	120.000
C21—C31—C41	120.00	C22—C32—C42	120.00
C21—C31—Cl81	118.95 (6)	C22—C32—Cl82	118.91 (6)
C41—C31—Cl81	121.04 (6)	C42—C32—Cl82	121.06 (6)
C31—C41—C51	120.00	C32—C42—C52	120.00
C31—C41—H41	120.000	C32—C42—H42	120.000
C51—C41—H41	120.000	C52—C42—H42	120.000
C41—C51—C61	120.00	C42—C52—C62	120.00
C41—C51—H51	120.000	C42—C52—H52	120.000
C61—C51—H51	120.000	C62—C52—H52	120.000
C11—C61—C51	120.00	C12—C62—C52	120.00
C11—C61—H61	120.000	C12—C62—H62	120.000
C51—C61—H61	120.000	C52—C62—H62	120.000
C11—O71—H71	114.868	C12—O72—H72	114.913

(4CL1)

Crystal data

C6H5ClO	F(000) = 528
Mr = 128.56	Dx = 1.455 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.7086 (11) Å	Cell parameters from 3307 reflections
b = 15.4523 (19) Å	θ = 2–29°
c = 8.7414 (11) Å	µ = 0.53 mm^−1
β = 93.954 (2)°	T = 150 K
V = 1173.5 (3) Å^3	Block, colourless
Z = 8	0.44 × 0.38 × 0.25 mm

Data collection

Bruker SMART diffractometer	2442 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ω scans	θmax = 28.8°, θmin = 2.3°
Absorption correction: multi-scan SADABS (Siemens, 1996)	h = −9→11
Tmin = 0.69, Tmax = 0.88	k = −20→19
7471 measured reflections	l = −11→10
2839 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.039	P = P(6)*max(Fo^2,0) + (1-P(6))Fc^2 Method = SHELXL 97 (Sheldrick, 1997) W = 1. / [Sigma^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)Sin(theta)] P(i) are: 0.684E-01 0.725 0.00 0.00 0.00 0.333
wR(F^2) = 0.101	(Δ/σ)max = 0.001
S = 0.74	Δρmax = 0.33 e Å^−3
2839 reflections	Δρmin = −0.31 e Å^−3
152 parameters	Extinction correction: Larson 1970 Crystallographic Computing eq 22
2 restraints	Extinction coefficient: 45 (11)
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C11	1.06333 (17)	0.86425 (11)	0.17530 (18)	0.0249
C21	1.16611 (19)	0.85202 (11)	0.0632 (2)	0.0291
C31	1.2470 (2)	0.92194 (12)	0.01072 (19)	0.0308
C41	1.22279 (18)	1.00316 (11)	0.07053 (19)	0.0271
C51	1.11976 (19)	1.01599 (11)	0.18165 (19)	0.0284
C61	1.03955 (18)	0.94587 (11)	0.23426 (19)	0.0272
O71	0.98528 (14)	0.79260 (8)	0.22328 (14)	0.0304
Cl81	1.32180 (5)	1.09146 (3)	0.00165 (5)	0.0380
C12	0.69379 (17)	0.67154 (10)	0.01969 (18)	0.0238
C22	0.62387 (19)	0.70668 (11)	0.14329 (18)	0.0278
C32	0.47123 (19)	0.68836 (11)	0.16344 (19)	0.0282
C42	0.39015 (18)	0.63485 (10)	0.06042 (19)	0.0256
C52	0.4581 (2)	0.60033 (11)	−0.06413 (19)	0.0281
C62	0.61153 (19)	0.61851 (10)	−0.08394 (19)	0.0277
O72	0.84562 (14)	0.68764 (8)	−0.00399 (14)	0.0315
Cl82	0.19921 (5)	0.61016 (3)	0.08950 (5)	0.0353
H71	0.942 (3)	0.8050 (16)	0.300 (2)	0.0500*
H72	0.885 (3)	0.7164 (15)	0.066 (3)	0.0500*
H21	1.1811	0.7959	0.0224	0.0351*
H31	1.3183	0.9141	−0.0656	0.0373*
H51	1.1041	1.0723	0.2215	0.0339*
H61	0.9684	0.9538	0.3107	0.0328*
H22	0.6807	0.7432	0.2139	0.0335*
H32	0.4225	0.7124	0.2476	0.0342*
H52	0.4004	0.5646	−0.1354	0.0336*
H62	0.6600	0.5946	−0.1684	0.0335*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C11	0.0220 (7)	0.0286 (8)	0.0240 (7)	−0.0004 (6)	0.0013 (6)	0.0016 (6)
C21	0.0295 (8)	0.0290 (8)	0.0293 (8)	0.0030 (7)	0.0066 (6)	−0.0022 (6)
C31	0.0292 (8)	0.0384 (9)	0.0256 (8)	0.0000 (7)	0.0071 (6)	0.0009 (7)
C41	0.0243 (7)	0.0320 (8)	0.0246 (8)	−0.0051 (6)	−0.0023 (6)	0.0045 (6)
C51	0.0291 (8)	0.0272 (8)	0.0285 (8)	0.0002 (6)	−0.0006 (6)	−0.0030 (6)
C61	0.0230 (7)	0.0332 (9)	0.0258 (8)	0.0017 (6)	0.0037 (6)	−0.0024 (6)
O71	0.0319 (6)	0.0299 (6)	0.0308 (7)	−0.0036 (5)	0.0107 (5)	−0.0008 (5)
Cl81	0.0403 (3)	0.0389 (3)	0.0346 (2)	−0.01376 (18)	0.00157 (18)	0.00619 (18)
C12	0.0238 (7)	0.0240 (7)	0.0241 (7)	0.0004 (6)	0.0048 (6)	0.0038 (6)
C22	0.0293 (8)	0.0295 (8)	0.0249 (8)	−0.0048 (6)	0.0049 (6)	−0.0044 (6)
C32	0.0288 (8)	0.0317 (8)	0.0250 (8)	−0.0013 (6)	0.0084 (6)	−0.0018 (6)
C42	0.0234 (7)	0.0258 (8)	0.0278 (8)	−0.0020 (6)	0.0043 (6)	0.0048 (6)
C52	0.0313 (8)	0.0270 (8)	0.0257 (8)	−0.0030 (6)	−0.0009 (6)	−0.0006 (6)
C62	0.0325 (8)	0.0274 (8)	0.0239 (8)	0.0007 (6)	0.0076 (6)	−0.0018 (6)
O72	0.0261 (6)	0.0380 (7)	0.0314 (6)	−0.0047 (5)	0.0089 (5)	−0.0057 (5)
Cl82	0.0253 (2)	0.0422 (3)	0.0387 (3)	−0.00696 (17)	0.00520 (17)	0.00136 (18)

Geometric parameters (Å, º)

C11—C21	1.385 (2)	C12—C22	1.387 (2)
C11—C61	1.383 (2)	C12—C62	1.384 (2)
C11—O71	1.3795 (19)	C12—O72	1.3750 (18)
C21—C31	1.385 (2)	C22—C32	1.382 (2)
C21—H21	0.950	C22—H22	0.950
C31—C41	1.381 (2)	C32—C42	1.380 (2)
C31—H31	0.950	C32—H32	0.950
C41—C51	1.381 (2)	C42—C52	1.381 (2)
C41—Cl81	1.7433 (17)	C42—Cl82	1.7416 (16)
C51—C61	1.385 (2)	C52—C62	1.388 (2)
C51—H51	0.950	C52—H52	0.950
C61—H61	0.950	C62—H62	0.950
O71—H71	0.815 (19)	O72—H72	0.816 (19)
C21—C11—C61	120.58 (15)	C22—C12—C62	120.43 (14)
C21—C11—O71	117.49 (15)	C22—C12—O72	121.66 (14)
C61—C11—O71	121.93 (14)	C62—C12—O72	117.92 (14)
C11—C21—C31	119.74 (16)	C12—C22—C32	119.79 (15)
C11—C21—H21	120.132	C12—C22—H22	120.105
C31—C21—H21	120.133	C32—C22—H22	120.106
C21—C31—C41	119.28 (15)	C22—C32—C42	119.52 (15)
C21—C31—H31	120.358	C22—C32—H32	120.242
C41—C31—H31	120.358	C42—C32—H32	120.241
C31—C41—C51	121.33 (15)	C32—C42—C52	121.19 (15)
C31—C41—Cl81	119.24 (13)	C32—C42—Cl82	119.11 (13)
C51—C41—Cl81	119.42 (13)	C52—C42—Cl82	119.69 (13)
C41—C51—C61	119.22 (15)	C42—C52—C62	119.23 (15)
C41—C51—H51	120.391	C42—C52—H52	120.386
C61—C51—H51	120.391	C62—C52—H52	120.386
C51—C61—C11	119.85 (15)	C52—C62—C12	119.83 (14)
C51—C61—H61	120.077	C52—C62—H62	120.084
C11—C61—H61	120.077	C12—C62—H62	120.083
C11—O71—H71	109.2 (18)	C12—O72—H72	110.4 (17)

(4CL2)

Crystal data

C6H5ClO	F(000) = 528
Mr = 128.56	Dx = 1.462 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 3.9724 (5) Å	Cell parameters from 2464 reflections
b = 12.7328 (17) Å	θ = 3–28°
c = 23.155 (3) Å	µ = 0.54 mm^−1
β = 94.126 (2)°	T = 150 K
V = 1168.2 (3) Å^3	Colourless, plate
Z = 8	0.70 × 0.50 × 0.36 mm

Data collection

Bruker SMART diffractometer	2219 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ω scans	θmax = 28.9°, θmin = 1.8°
Absorption correction: multi-scan SADABS (Siemens, 1996)	h = −4→5
Tmin = 0.49, Tmax = 0.82	k = −14→17
7449 measured reflections	l = −31→29
2843 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.110	P = P(6)*max(Fo^2,0) + (1-P(6))Fc^2 Method = SHELXL 97 (Sheldrick, 1997) W = 1. / [Sigma^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)Sin(theta)] P(i) are: 0.700E-01 0.890 0.00 0.00 0.00 0.333
S = 0.75	(Δ/σ)max = 0.001
2843 reflections	Δρmax = 0.44 e Å^−3
151 parameters	Δρmin = −0.44 e Å^−3
2 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C11	1.0131 (5)	0.59662 (16)	0.37175 (8)	0.0252
C21	0.9419 (5)	0.70294 (16)	0.37324 (8)	0.0251
C31	1.0331 (5)	0.76729 (15)	0.32892 (9)	0.0259
C41	1.1906 (5)	0.72440 (17)	0.28330 (8)	0.0261
C51	1.2588 (5)	0.61826 (17)	0.28103 (9)	0.0294
C61	1.1694 (5)	0.55424 (16)	0.32553 (9)	0.0294
O71	0.9285 (4)	0.52928 (12)	0.41504 (6)	0.0344
Cl81	1.31142 (14)	0.80703 (5)	0.22847 (2)	0.0368
C12	0.6315 (5)	0.70387 (15)	0.53908 (8)	0.0239
C22	0.4419 (5)	0.77671 (16)	0.50664 (8)	0.0259
C32	0.3853 (5)	0.87501 (16)	0.52983 (10)	0.0295
C42	0.5209 (5)	0.89835 (15)	0.58478 (9)	0.0289
C52	0.7130 (5)	0.82661 (16)	0.61705 (8)	0.0285
C62	0.7690 (5)	0.72826 (16)	0.59388 (8)	0.0270
O72	0.6774 (4)	0.60666 (11)	0.51475 (6)	0.0315
Cl82	0.44248 (17)	1.02081 (4)	0.61477 (3)	0.0466
H71	0.842 (7)	0.561 (2)	0.4395 (11)	0.0500*
H72	0.777 (7)	0.570 (2)	0.5385 (12)	0.0500*
H21	0.8307	0.7316	0.4046	0.0301*
H31	0.9876	0.8405	0.3299	0.0309*
H51	1.3660	0.5896	0.2492	0.0353*
H61	1.2151	0.4811	0.3245	0.0352*
H22	0.3510	0.7596	0.4687	0.0311*
H32	0.2544	0.9257	0.5081	0.0356*
H52	0.8061	0.8442	0.6548	0.0343*
H62	0.9015	0.6779	0.6156	0.0326*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C11	0.0252 (10)	0.0276 (10)	0.0224 (9)	0.0025 (8)	−0.0017 (7)	−0.0004 (7)
C21	0.0254 (10)	0.0276 (10)	0.0223 (9)	0.0047 (8)	0.0014 (7)	−0.0050 (7)
C31	0.0249 (10)	0.0230 (9)	0.0293 (10)	0.0022 (7)	−0.0022 (8)	−0.0017 (8)
C41	0.022 (1)	0.0332 (10)	0.0222 (9)	−0.0032 (8)	−0.0008 (7)	0.0017 (8)
C51	0.0288 (11)	0.0334 (11)	0.0261 (10)	0.0039 (8)	0.0023 (8)	−0.0063 (8)
C61	0.0323 (11)	0.0251 (10)	0.0308 (10)	0.0041 (8)	0.0011 (8)	−0.0049 (8)
O71	0.0484 (10)	0.0278 (8)	0.0279 (8)	0.0082 (7)	0.0086 (7)	0.0036 (6)
Cl81	0.0360 (3)	0.0441 (3)	0.0306 (3)	−0.0003 (2)	0.0043 (2)	0.0097 (2)
C12	0.0269 (10)	0.0214 (9)	0.0245 (9)	−0.0018 (7)	0.0087 (7)	−0.0008 (7)
C22	0.0257 (10)	0.0267 (10)	0.0253 (9)	−0.0004 (8)	0.0027 (8)	0.0010 (8)
C32	0.0253 (10)	0.0253 (10)	0.0386 (11)	0.0037 (8)	0.0060 (8)	0.0037 (8)
C42	0.0284 (10)	0.0205 (9)	0.0394 (11)	−0.0024 (8)	0.0134 (8)	−0.0059 (8)
C52	0.0329 (11)	0.0279 (10)	0.0251 (9)	−0.0065 (8)	0.0055 (8)	−0.0027 (8)
C62	0.0293 (11)	0.0265 (10)	0.0258 (10)	0.0003 (8)	0.0049 (8)	0.0032 (8)
O72	0.0466 (9)	0.0218 (7)	0.0264 (7)	0.0041 (6)	0.0044 (6)	−0.0015 (6)
Cl82	0.0538 (4)	0.0260 (3)	0.0620 (4)	0.0017 (2)	0.0183 (3)	−0.0140 (3)

Geometric parameters (Å, º)

C11—C21	1.384 (3)	C12—C22	1.382 (3)
C11—C61	1.385 (3)	C12—C62	1.380 (3)
C11—O71	1.379 (2)	C12—O72	1.377 (2)
C21—C31	1.382 (3)	C22—C32	1.387 (3)
C21—H21	0.950	C22—H22	0.950
C31—C41	1.379 (3)	C32—C42	1.378 (3)
C31—H31	0.950	C32—H32	0.950
C41—C51	1.380 (3)	C42—C52	1.376 (3)
C41—Cl81	1.743 (2)	C42—Cl82	1.744 (2)
C51—C61	1.380 (3)	C52—C62	1.387 (3)
C51—H51	0.950	C52—H52	0.950
C61—H61	0.950	C62—H62	0.950
O71—H71	0.79 (2)	O72—H72	0.81 (3)
C21—C11—C61	120.28 (19)	C22—C12—C62	120.86 (18)
C21—C11—O71	121.95 (18)	C22—C12—O72	117.63 (18)
C61—C11—O71	117.76 (18)	C62—C12—O72	121.52 (18)
C11—C21—C31	119.77 (18)	C12—C22—C32	119.50 (19)
C11—C21—H21	120.125	C12—C22—H22	120.247
C31—C21—H21	120.107	C32—C22—H22	120.254
C21—C31—C41	119.47 (18)	C22—C32—C42	119.26 (19)
C21—C31—H31	120.267	C22—C32—H32	120.366
C41—C31—H31	120.264	C42—C32—H32	120.375
C31—C41—C51	121.20 (19)	C32—C42—C52	121.53 (19)
C31—C41—Cl81	118.89 (16)	C32—C42—Cl82	119.43 (17)
C51—C41—Cl81	119.90 (16)	C52—C42—Cl82	119.03 (17)
C41—C51—C61	119.23 (18)	C42—C52—C62	119.19 (19)
C41—C51—H51	120.384	C42—C52—H52	120.404
C61—C51—H51	120.388	C62—C52—H52	120.410
C11—C61—C51	120.04 (19)	C52—C62—C12	119.66 (19)
C11—C61—H61	119.976	C52—C62—H62	120.172
C51—C61—H61	119.986	C12—C62—H62	120.167
C11—O71—H71	110 (2)	C12—O72—H72	109 (2)

(4CL2P)

Crystal data

C6H5ClO	F(000) = 528
Mr = 128.56	Dx = 1.408 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 4.1096 (4) Å	Cell parameters from 1170 reflections
b = 12.7665 (10) Å	θ = 3–19°
c = 23.181 (3) Å	µ = 0.52 mm^−1
β = 94.201 (14)°	T = 293 K
V = 1212.9 (2) Å^3	Block, colourless
Z = 8	0.30 × 0.30 × 0.18 mm

Data collection

Bruker SMART diffractometer	397 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
ω scans	θmax = 23.2°, θmin = 3.2°
Absorption correction: multi-scan SADABS (Siemens, 1996)	h = −4→4
Tmin = 0.68, Tmax = 0.91	k = 0→14
7359 measured reflections	l = 0→10
711 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.055	H-atom parameters not refined
wR(F^2) = 0.160	P = P(6)*max(Fo^2,0) + (1-P(6))Fc^2 Method = SHELXL 97 (Sheldrick, 1997) W = 1. / [Sigma^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)Sin(theta)] P(i) are: 0.625E-01 1.91 0.00 0.00 0.00 0.333
S = 1.03	(Δ/σ)max = 0.007
710 reflections	Δρmax = 0.21 e Å^−3
61 parameters	Δρmin = −0.20 e Å^−3
64 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C11	1.0109	0.5962	0.3713	0.072 (2)*
C21	0.9446	0.7028	0.3736	0.067 (2)*
C31	1.0353	0.7686	0.3298	0.060 (2)*
C41	1.1923	0.7278	0.2836	0.070 (2)*
C51	1.2586	0.6211	0.2813	0.084 (3)*
C61	1.1679	0.5553	0.3252	0.079 (3)*
O71	0.9233 (13)	0.52747 (8)	0.4157 (2)	0.0783
Cl81	1.3116 (5)	0.80847 (15)	0.23084 (16)	0.1012
C12	0.6344	0.7025	0.5402	0.062 (2)*
C22	0.4402	0.7740	0.5082	0.071 (2)*
C32	0.3805	0.8722	0.5310	0.069 (2)*
C42	0.5149	0.8990	0.5858	0.067 (2)*
C52	0.7090	0.8276	0.6178	0.079 (3)*
C62	0.7688	0.7293	0.5950	0.070 (2)*
O72	0.6886 (13)	0.6083 (2)	0.51791 (13)	0.1113
Cl82	0.4331 (7)	1.01825 (15)	0.61446 (12)	0.1271
H71	0.8565	0.5485	0.4458	0.0500*
H72	0.8183	0.5626	0.5359	0.1047*
H21	0.8373	0.7307	0.4051	0.0800*
H31	0.9900	0.8415	0.3313	0.0721*
H51	1.3659	0.5932	0.2498	0.1012*
H61	1.2132	0.4825	0.3236	0.0951*
H22	0.3483	0.7556	0.4708	0.0850*
H32	0.2478	0.9211	0.5091	0.0832*
H52	0.8009	0.8459	0.6552	0.0951*
H62	0.9015	0.6805	0.6168	0.0840*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O71	0.125 (5)	0.086 (4)	0.03 (3)	0.013 (3)	0.035 (8)	0.008 (5)
Cl81	0.1012 (17)	0.1153 (18)	0.087 (12)	−0.0038 (12)	0.009 (3)	0.026 (2)
O72	0.123 (4)	0.050 (3)	0.16 (2)	0.011 (3)	−0.016 (7)	−0.006 (5)
Cl82	0.144 (2)	0.0714 (13)	0.172 (12)	0.0035 (12)	0.050 (3)	−0.028 (2)

Geometric parameters (Å, º)

C11—C21	1.39	C12—C22	1.39
C11—C61	1.39	C12—C62	1.39
C11—O71	1.418 (3)	C12—O72	1.334 (2)
C21—C31	1.39	C22—C32	1.39
C21—H21	0.950	C22—H22	0.950
C31—C41	1.39	C32—C42	1.39
C31—H31	0.950	C32—H32	0.950
C41—C51	1.39	C42—C52	1.39
C41—Cl81	1.699 (3)	C42—Cl82	1.704 (2)
C51—C61	1.39	C52—C62	1.39
C51—H51	0.950	C52—H52	0.950
C61—H61	0.950	C62—H62	0.950
O71—H71	0.815	O72—H72	0.875
C21—C11—C61	120.00	C22—C12—C62	120.00
C21—C11—O71	121.11 (7)	C22—C12—O72	119.39 (6)
C61—C11—O71	118.89 (7)	C62—C12—O72	120.61 (6)
C11—C21—C31	120.00	C12—C22—C32	120.00
C11—C21—H21	120.000	C12—C22—H22	120.000
C31—C21—H21	120.000	C32—C22—H22	120.000
C21—C31—C41	120.00	C22—C32—C42	120.00
C21—C31—H31	120.000	C22—C32—H32	120.000
C41—C31—H31	120.000	C42—C32—H32	120.000
C31—C41—C51	120.00	C32—C42—C52	120.00
C31—C41—Cl81	120.08 (6)	C32—C42—Cl82	119.99 (7)
C51—C41—Cl81	119.90 (6)	C52—C42—Cl82	119.99 (7)
C41—C51—C61	120.00	C42—C52—C62	120.00
C41—C51—H51	120.000	C42—C52—H52	120.000
C61—C51—H51	120.000	C62—C52—H52	120.000
C11—C61—C51	120.00	C12—C62—C52	120.00
C11—C61—H61	120.000	C12—C62—H62	120.000
C51—C61—H61	120.000	C52—C62—H62	120.000
C11—O71—H71	122.525	C12—O72—H72	121.943

(2F1)

Crystal data

C6H5FO	F(000) = 696
Mr = 112.10	Dx = 1.392 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.1336 (10) Å	Cell parameters from 2044 reflections
b = 8.2766 (5) Å	θ = 2–26°
c = 11.4975 (7) Å	µ = 0.12 mm^−1
β = 100.234 (2)°	T = 150 K
V = 1604.50 (17) Å^3	Cylinder, colourless
Z = 12	1.00 × 0.38 × 0.38 mm

Data collection

Bruker SMART diffractometer	1302 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ω scans	θmax = 28.7°, θmin = 2.4°
Absorption correction: multi-scan SADABS (Siemens, 1996)	h = −22→22
Tmin = 0.575, Tmax = 1.000	k = −10→11
7505 measured reflections	l = −15→15
1957 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.056	P = P(6)*max(Fo^2,0) + (1-P(6))Fc^2 Method = SHELXL 97 (Sheldrick, 1997) W = 1. / [Sigma^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)Sin(theta)] P(i) are: 0.172E-01 1.34 0.00 0.00 0.00 0.333
wR(F^2) = 0.111	(Δ/σ)max = 0.000179
S = 1.08	Δρmax = 0.32 e Å^−3
1956 reflections	Δρmin = −0.40 e Å^−3
125 parameters	Extinction correction: Larson 1970 Crystallographic Computing eq 22
14 restraints	Extinction coefficient: 29 (9)
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C11	0.63513 (11)	0.0773 (3)	0.59162 (18)	0.0371
C21	0.66814 (13)	−0.0140 (3)	0.5134 (2)	0.0457
C31	0.74867 (14)	−0.0170 (3)	0.5146 (2)	0.0545
C41	0.79752 (13)	0.0740 (4)	0.5970 (2)	0.0560
C51	0.76568 (13)	0.1655 (4)	0.6765 (2)	0.0542
C61	0.68456 (13)	0.1672 (3)	0.67446 (19)	0.0446
O71	0.55429 (9)	0.0768 (2)	0.58623 (14)	0.0443
F81	0.61874 (8)	−0.1033 (2)	0.43296 (13)	0.0707
C12	0.5000	0.4249 (4)	0.7500	0.0319
C22	0.53050 (11)	0.5110 (3)	0.66635 (18)	0.0377
C32	0.53071 (13)	0.6767 (3)	0.6650 (2)	0.0484
C42	0.5000	0.7589 (4)	0.7500	0.0560
O72	0.5000	0.2598 (3)	0.7500	0.0454
F82	0.56421 (14)	0.4402 (3)	0.5881 (2)	0.0438	0.5000
H72	0.511 (3)	0.214 (6)	0.694 (4)	0.0500*	0.5000
H71	0.541 (3)	0.145 (5)	0.632 (4)	0.0527*	0.5000
H712	0.527 (2)	0.032 (6)	0.527 (3)	0.0527*	0.5000
H31	0.7701	−0.0811	0.4593	0.0665*
H41	0.8532	0.0737	0.5990	0.0666*
H51	0.7996	0.2284	0.7335	0.0635*
H61	0.6631	0.2304	0.7302	0.0531*
H32	0.5519	0.7337	0.6059	0.0566*
H42	0.5000	0.8737	0.7500	0.0645*
H62	0.5521	0.4541	0.6077	0.0449*	0.5000

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C11	0.0317 (10)	0.0416 (13)	0.0380 (12)	−0.0015 (10)	0.0063 (9)	0.0065 (10)
C21	0.0365 (12)	0.0536 (15)	0.0462 (13)	−0.0059 (11)	0.0048 (10)	−0.0052 (12)
C31	0.0407 (12)	0.0704 (18)	0.0553 (15)	0.0058 (13)	0.0160 (11)	−0.0029 (14)
C41	0.0303 (11)	0.083 (2)	0.0535 (15)	0.0011 (13)	0.0037 (11)	0.0092 (15)
C51	0.0368 (12)	0.0772 (19)	0.0447 (14)	−0.0074 (12)	−0.0035 (11)	0.0023 (13)
C61	0.0389 (12)	0.0545 (15)	0.0393 (13)	−0.0008 (11)	0.0044 (10)	−0.0013 (11)
O71	0.0310 (8)	0.0479 (11)	0.0544 (11)	−0.0031 (7)	0.0084 (7)	−0.0049 (8)
F81	0.0471 (8)	0.0907 (12)	0.0761 (10)	−0.0108 (8)	0.0159 (7)	−0.0408 (10)
C12	0.0267 (13)	0.0319 (16)	0.0356 (15)	0.0000	0.0012 (11)	0.0000
C22	0.0297 (10)	0.0443 (13)	0.0383 (12)	0.0039 (10)	0.0043 (9)	0.0079 (11)
C32	0.0439 (13)	0.0409 (14)	0.0567 (15)	−0.0054 (11)	−0.0009 (11)	0.0184 (12)
C42	0.059 (2)	0.0324 (19)	0.070 (3)	0.0000	−0.0073 (19)	0.0000
O72	0.0623 (15)	0.0312 (13)	0.0416 (14)	0.0000	0.0065 (12)	0.0000
F82	0.0513 (14)	0.0443 (16)	0.0399 (14)	0.0068 (12)	0.0194 (11)	0.0049 (12)

Geometric parameters (Å, º)

C11—C21	1.371 (3)	O71—H712	0.836 (19)
C11—C61	1.375 (3)	C12—C22^i	1.373 (2)
C11—O71	1.375 (2)	C12—C22	1.373 (2)
C21—C31	1.378 (3)	C12—O72	1.366 (4)
C21—F81	1.357 (2)	C22—C32	1.372 (3)
C31—C41	1.372 (3)	C22—F82	1.293 (3)
C31—H31	0.950	C22—H62	0.950
C41—C51	1.373 (4)	C32—C42	1.371 (3)
C41—H41	0.950	C32—H32	0.950
C51—C61	1.386 (3)	C42—H42	0.950
C51—H51	0.950	O72—H72^i	0.80 (3)
C61—H61	0.950	O72—H72	0.80 (3)
O71—H71	0.830 (19)
C21—C11—C61	118.51 (19)	H71—O71—H712	129 (5)
C21—C11—O71	119.87 (19)	C22^i—C12—C22	117.5 (3)
C61—C11—O71	121.6 (2)	C22^i—C12—O72	121.27 (14)
C11—C21—C31	122.2 (2)	C22—C12—O72	121.27 (14)
C11—C21—F81	117.86 (18)	C12—C22—C32	122.0 (2)
C31—C21—F81	120.0 (2)	C12—C22—F82	121.7 (2)
C21—C31—C41	118.9 (2)	C32—C22—F82	116.3 (2)
C21—C31—H31	120.534	C12—C22—H62	119.020
C41—C31—H31	120.529	C32—C22—H62	119.018
C31—C41—C51	119.8 (2)	F82—C22—H62	4.045
C31—C41—H41	120.110	C22—C32—C42	119.1 (2)
C51—C41—H41	120.108	C22—C32—H32	120.461
C41—C51—C61	120.7 (2)	C42—C32—H32	120.458
C41—C51—H51	119.663	C32—C42—C32^i	120.5 (3)
C61—C51—H51	119.655	C32—C42—H42	119.769
C51—C61—C11	119.9 (2)	C32^i—C42—H42	119.769
C51—C61—H61	120.048	C12—O72—H72^i	118 (4)
C11—C61—H61	120.048	C12—O72—H72	118 (4)
C11—O71—H71	111 (3)	H72^i—O72—H72	123 (7)
C11—O71—H712	117 (3)

Symmetry code: (i) −x+1, y, −z+3/2.

(2F2P)

Crystal data

C6H5FO	Dx = 1.458 Mg m^−3
Mr = 112.10	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 397 reflections
a = 5.7168 (7) Å	θ = 3–20°
b = 9.9997 (19) Å	µ = 0.12 mm^−1
c = 17.868 (2) Å	T = 403 K
V = 1021.4 (3) Å^3	Colourless, plate
Z = 8	0.30 × 0.30 × 0.18 mm
F(000) = 464

Data collection

Bruker SMART diffractometer	261 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.099
ω scans	θmax = 23.3°, θmin = 3.1°
Absorption correction: multi-scan SADABS (Siemens, 1996)	h = 0→6
Tmin = 0.96, Tmax = 0.98	k = 0→5
3070 measured reflections	l = 0→19
469 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.083	P = P(6)*max(Fo^2,0) + (1-P(6))Fc^2 Method = SHELXL 97 (Sheldrick, 1997) W = 1. / [Sigma^2(F^2) + (P(1)p)^2 + P(2)p + P(4) + P(5)Sin(theta)] P(i) are: 0.173 0.00 0.00 0.00 0.00 0.333
wR(F^2) = 0.251	(Δ/σ)max = 0.001
S = 0.94	Δρmax = 0.27 e Å^−3
461 reflections	Δρmin = −0.20 e Å^−3
62 parameters	Absolute structure: Flack, 0 Friedel-pairs
64 restraints	Absolute structure parameter: −2 (7)
Primary atom site location: simulated annealing

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O71	−0.0148 (9)	0.1191 (6)	0.4817 (3)	0.1063
F81	0.0058 (10)	−0.0482 (6)	0.3630 (3)	0.1228
O72	−0.1484 (8)	0.2974 (7)	0.6168 (3)	0.0811
F82	0.2395 (8)	0.1434 (10)	0.6241 (3)	0.1001
H72	−0.1167	0.2361	0.5826	0.0893*
H71	0.1032	0.1227	0.4494	0.1108*
C11	−0.1810	0.0265	0.4703	0.077 (3)*
C21	−0.1667	−0.0579	0.4086	0.073 (3)*
C31	−0.3380	−0.1542	0.3967	0.089 (4)*
C41	−0.5238	−0.1661	0.4465	0.090 (4)*
C51	−0.5381	−0.0818	0.5081	0.083 (4)*
C61	−0.3667	0.0145	0.5200	0.074 (3)*
C12	0.0036	0.3138	0.6719	0.058 (3)*
C22	0.2033	0.2347	0.6748	0.064 (3)*
C32	0.3634	0.2514	0.7326	0.088 (4)*
C42	0.3239	0.3472	0.7875	0.078 (4)*
C52	0.1242	0.4264	0.7846	0.088 (4)*
C62	−0.0359	0.4097	0.7268	0.083 (4)*
H31	−0.3282	−0.2118	0.3546	0.1063*
H41	−0.6409	−0.2320	0.4383	0.1081*
H51	−0.6650	−0.0900	0.5422	0.0994*
H61	−0.3766	0.0722	0.5622	0.0890*
H32	0.4999	0.1973	0.7346	0.1056*
H42	0.4333	0.3587	0.8270	0.0940*
H52	0.0971	0.4919	0.8222	0.1055*
H62	−0.1724	0.4638	0.7249	0.0995*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O71	0.087 (5)	0.15 (3)	0.084 (5)	−0.017 (9)	0.011 (4)	−0.002 (7)
F81	0.108 (4)	0.18 (2)	0.082 (4)	0.001 (8)	0.018 (3)	−0.025 (6)
O72	0.089 (5)	0.08 (2)	0.077 (4)	−0.001 (8)	−0.015 (4)	−0.012 (5)
F82	0.113 (5)	0.088 (19)	0.099 (4)	−0.004 (7)	0.022 (4)	−0.028 (6)

Geometric parameters (Å, º)

O71—H71	0.888	C51—C61	1.39
O71—C11	1.343 (2)	C51—H51	0.950
F81—C21	1.283 (5)	C61—H61	0.950
O72—H72	0.885	C12—C22	1.39
O72—C12	1.324 (2)	C12—C62	1.39
F82—C22	1.303 (7)	C22—C32	1.39
C11—C21	1.39	C32—C42	1.39
C11—C61	1.39	C32—H32	0.950
C21—C31	1.39	C42—C52	1.39
C31—C41	1.39	C42—H42	0.950
C31—H31	0.950	C52—C62	1.39
C41—C51	1.39	C52—H52	0.950
C41—H41	0.950	C62—H62	0.950
H71—O71—C11	117.800	C51—C61—H61	120.000
H72—O72—C12	117.782	O72—C12—C22	119.74 (6)
O71—C11—C21	119.81 (6)	O72—C12—C62	120.26 (6)
O71—C11—C61	120.19 (6)	C22—C12—C62	120.00
C21—C11—C61	120.00	C12—C22—F82	120.23 (7)
C11—C21—F81	120.20 (7)	C12—C22—C32	120.00
C11—C21—C31	120.00	F82—C22—C32	119.76 (7)
F81—C21—C31	119.80 (7)	C22—C32—C42	120.00
C21—C31—C41	120.00	C22—C32—H32	120.000
C21—C31—H31	120.000	C42—C32—H32	120.000
C41—C31—H31	120.000	C32—C42—C52	120.00
C31—C41—C51	120.00	C32—C42—H42	120.000
C31—C41—H41	120.000	C52—C42—H42	120.000
C51—C41—H41	120.000	C42—C52—C62	120.00
C41—C51—C61	120.00	C42—C52—H52	120.000
C41—C51—H51	120.000	C62—C52—H52	120.000
C61—C51—H51	120.000	C52—C62—C12	120.00
C11—C61—C51	120.00	C52—C62—H62	120.000
C11—C61—H61	120.000	C12—C62—H62	120.000

 

Footnotes

¹Supplementary data for this paper are available from the IUCr electronic archives (Reference: BS5012 ). Services for accessing these data are described at the back of the journal.